U.S. patent number 4,237,253 [Application Number 05/897,435] was granted by the patent office on 1980-12-02 for copolymers, their process of preparation, and cosmetic compounds containing them.
This patent grant is currently assigned to L'Oreal. Invention is credited to Bernard Jacquet, Claude Mahieu, Christos Papantoniou.
United States Patent |
4,237,253 |
Jacquet , et al. |
December 2, 1980 |
**Please see images for:
( Certificate of Correction ) ** |
Copolymers, their process of preparation, and cosmetic compounds
containing them
Abstract
Copolymers having the formula ##STR1## where B represents Na, K,
NH.sub.4, ##STR2## or 2-amino-2-methylpropanol-1, R.sub.1 and
R.sub.2 represent hydrogen or -(X) OH; X represents an alkylene
having 1-3 carbon atoms or alkylene substituted by at least one
hydroxy methyl, M represents at least one unsaturated monomer
selected from acrylamides or methacrylamides substituted on the
nitrogen by alkyl, the acrylates or methacrylates of monoalkyl
ether of ethylene glycol or of polyethylene glycol, and
N-vinylpyrrolidone, x is 22-64 mole percent, y is 13-71 mole
percent, z is 6-23 mole percent, v is 0-22 mole percent and x+y+z+v
is equal to 100 mole percent, can be produced by copolymerizing
N,N-dimethylamino-2 ethyl methacrylate, methyl methacrylate,
methacrylic acid and optionally at least one other monomer
corresponding to M.
Inventors: |
Jacquet; Bernard (Antony,
FR), Mahieu; Claude (Paris, FR),
Papantoniou; Christos (Montmorency, FR) |
Assignee: |
L'Oreal (Paris,
FR)
|
Family
ID: |
26219974 |
Appl.
No.: |
05/897,435 |
Filed: |
April 18, 1978 |
Foreign Application Priority Data
|
|
|
|
|
Apr 21, 1977 [FR] |
|
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77 12048 |
Mar 14, 1978 [FR] |
|
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78 07308 |
|
Current U.S.
Class: |
525/326.9;
525/329.4; 526/311; 526/923; 525/328.4; 525/374; 526/208;
526/219.3; 526/264; 526/307.3; 526/312; 424/47; 526/75; 526/212;
526/216; 526/240; 526/304 |
Current CPC
Class: |
A61Q
5/06 (20130101); A61K 8/8152 (20130101); C08F
220/34 (20130101); C08F 220/14 (20130101); C08F
220/34 (20130101); C08F 220/14 (20130101); C08F
220/06 (20130101); C08F 220/14 (20130101); C08F
220/34 (20130101); C08F 220/06 (20130101); Y10S
526/923 (20130101) |
Current International
Class: |
A61K
8/72 (20060101); A61K 8/81 (20060101); A61Q
5/06 (20060101); C08F 220/14 (20060101); C08F
220/34 (20060101); C08F 220/00 (20060101); C08F
002/00 (); C08F 004/04 (); C08F 220/36 (); C08F
220/54 () |
Field of
Search: |
;526/240,303,304,311,312,264,923,75,208,216 ;424/47 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Erzin Editor, "Adv. in Chem. Series No. 125", ACS Wash., D.C. 1973,
Nakajima, Fractionation of Lin P.E with GPC, pp. 98-107. .
Billmeyer, "Chara. of M.W Dist. in High Polymers", J. Poly. Sci.
PTC #8, pp. 161-178, (1965). .
Chem. Abs. 163951k, Medrange et al. "Hair Cosmetics Cont.
Methacrylate Copoly", vol. 78, 1973..
|
Primary Examiner: Schofer; Joseph L.
Assistant Examiner: Lilling; Herbert J.
Attorney, Agent or Firm: Cushman, Darby & Cushman
Claims
We claim:
1. Copolymers characterized by the fact that they correspond to the
following general formula: ##STR11## where: B represents Na, K,
NH.sub.4, ##STR12## or 2-amino-2-methyl propanal-1 R.sub.1 and
R.sub.2, identical or different, represent an atom of hydrogen or
the radical--(X)--OH;
X represents an alkylene radical, branched or unbranched, having
from 1 to 3 atoms of carbon or an alkylene radical, branched or
unbranched, substituted by at least one hydroxymethyl radical;
M represents a type of at least one unsaturated monomer taken from
the group consisting of the acrylamides or methacrylamides
substituted on the nitrogen by an alkyl radical, branched or
unbranched, the acrylates or methacrylates of monoalkyl ether of
ethylene glycol or of polyethylene glycol, and
N-vinylpyrrolidone;
x is from 22% to 64% in moles,
y is from 13% to 71% in moles,
z is from 6% to 23% in moles, and
v is from 0% to 22% in moles,
x+y+z+v being equal to 100%.
2. Copolymers according to claim 1 wherein the acrylamides or
methacrylamides substituted on the nitrogen by a branched or
unbranched alkyl radical correspond to the formula: ##STR13##
where: R.sub.6 represents an alkyl radical, branched or unbranched,
having 1 to 11 carbon atoms; and
R.sub.3, R.sub.4, and R.sub.5, identical or different, represent
either a hydrogen atom or a methyl radical.
3. Copolymers according to either claim 1 or claim 2 characterized
further by the fact that the acrylamides or methacrylamides
substituted on the nitrogen by a branched or unbranched alkyl
radical are taken from the group consisting of: N-tertiobutyl
acrylamide, N-octyl acrylamide, N-decyl acrylamide, N-dodecyl
acrylamide, N-((dimethyl-1,1) butyl-1) acrylamide,
N-((dimethyl-1,1) pentyl-1) acrylamide, as well as the
corresponding methacrylamides.
4. Copolymers according to claim 1 characterized by the fact that
the acrylates or methacrylates of monalkylether of ethylene glycol
or of polyethylene glycol correspond to the formula: ##STR14##
where: R.sub.3 represents a hydrogen atom or a methyl radical,
R.sub.7 represents a methyl or ethyl radical, and
n is an integer between 1 and 12.
5. Copolymers according to claim 1 or claim 4 characterized further
by the fact that the acrylates or methacrylates of monoalkylether
of ethylene or polyethylene glycol are taken from a group
consisting of the acrylates and methacrylates of monomethyl or
ethyl ether of ethylene or of diethylene glycol, and the acrylates
and methacrylates of .omega.-methyl or ethyl polyethylene
glycol.
6. The process of preparing a copolymer of claim 1 including the
steps of: (1) preparing an ammonium methyacrylate of the formula
##STR15## where: R.sub.1, R.sub.2 and X have the same significance
as in claim 1, by reacting methacrylic acid with an amino alcohol
of the formula: ##STR16## and (2) copolymerizing the said ammonium
methacrylate with N,N-dimethylamino-2 ethyl methacrylate and
methylmethacrylate, the copolymerization being carried out in
solution, in mass, in suspension, or in emulsion in the presence of
a catalyst.
7. The process of claim 6 in which the amino alcohol is selected
from the group consisting of monoethanolamine; diethanolamine;
triethanolamine; isopropanolamine; diisopropanolamine; tri-amine;
amino-2 methyl-2 propanol-1; amino-2 methyl-2 propanediol-1,3; and
amino-2 hydroxymethyl-2 propanediol-1,3.
8. The process of claim 7 in which the reaction of said methacrylic
acid with said amino alcohol is carried out in an organic solvent
at a temperature between 0.degree. C. and 20.degree. C.
9. The process of claim 8 in which the organic solvent is ethyl
ether or alcohol.
10. The process of claim 6 in which the said copolymerization is
performed in the solvent employed in the reaction of methacrylic
acid with said amino alcohol without previous isolation of the
ammonium methacrylate.
11. The process of preparing a copolymer of claim 1 including the
steps of: (1) copolymerizing in solution, in mass, in suspension or
in emulsion, in the presence of a catalyst, a mixture of (i)
N,N-dimethylamino-2 ethyl methacrylate, (ii) methyl methacrylate,
(iii) methacrylic acid, and and (2) neutralizing the carboxylic
acid functions of the copolymer obtained by means of an organic or
inorganic base.
12. The process of claim 11 in which the organic or inorganic base
is selected from the group consisting of sodium hydroxide;
potassium hydroxide; ammonium hydroxide; monoethanolamine;
diethanolamine; triethanolamine; isopropanolamine;
diisopropanolamine; tri amine; amino-2 methyl-2 propanol-1; amino-2
methyl-2 propanediol-1,3; and amino-2 hydroxymethyl-2
propanediol-1,3.
13. The process of claim 11 in which the polymerization is carried
out in a solvent selected from the group consisting of cyclohexane,
methylethylketone, heptane and ethyl acetate.
14. The process of claim 6 or claim 12 in which the
copolymerization is carried out at a temperature between about
55.degree. C. to 85.degree. C. for 6 to 24 hours.
15. The process of claim 6 or claim 12 in which the catalyst is
present in a proportion between 0.1% and 6% with respect to the
total weight of the monomers used in the reaction.
16. The process of claim 11 wherein said mixture also includes at
least one other monomer corresponding to radical M, wherein M
represents a type of at least one usaturated monomer selected from
the group consisting of acrylamide or methacrylamide substituted on
the nitrogen by an alkyl radical, branched or unbranched, the
acrylates or methacrylates of monoalkyl ether of ethylene glycol or
of polyethylene glycol, and N-vinylpyrrolidone.
17. The process of claim 6 wherein said ammonium methacrylate is
also copolymerized with at least one other monomer corresponding to
radical M, wherein M represents a type of at least one unsaturated
monomer selected from the group consisting of acrylamide or
methacrylamide substituted on the nitrogen by an alkyl radical,
branched or unbranched, the acrylates or methacrylates of monoalkyl
ether of ethylene glycol or of polyethylene glycol, and
N-vinylpyrrolidone.
Description
The present invention concerns new copolymers, a process of
preparing said copolymers and cosmetic compositions containing
them, in particular lacquers and waving lotions.
During recent years numerous synthetic polymers have been proposed
for use in compositions for the hair such as lacquers and waving
lotions.
In fact, previously used polymers did not give total satisfaction
to their (feminine) users because they presented certain
disadvantages that limited their regular use.
In particular, either a strong hygroscopicity causing a gluing
effect or an unesthetic appearance of the hair or an increased
friability of the copolymers entailing the consequent formation of
films is experienced on use of said polymers.
The new polymers that have been proposed recently provide remedies
for those disadvantages in part, but pose, on the other hand, some
problems in formulating the lacquers and waving lotions on account
of the lack of solubility of said polymers in certain solvents.
Among the polymers in particular these has been proposed the use of
polymers containing functions of quaternized tertiary amines such
as those described in the French Pat. No. 72 32244, polymers
resulting from the copolymerization of methyl methacrylate,
methacrylate of quaternized dimethylaminoethyl, and octadecyl
methacrylate.
Polymers of this type are proven to present a good affinity for
hair but they lack brilliance and good mechanical properties.
Furthermore, they are not easily compatible with certain propulsive
agents used in lacquers.
With the object in part of remedying these serious disadvantages
and also satisfying users, the synthesis of new copolymers in which
at least three constituent monomers have the methacrylic structure
has been perfected. In fact, it has been established that these
copolymers answer the set of requirements formulated by users and
by cosmeticians charged with developing cosmetic compounds such as
lacquers and waving lotions.
The copolymers of the invention are indeed endowed with excellent
solubility in ethanol and hydroethanolic mixtures; moreover, they
exhibit good compatibility with propulsive agents used in the
aerosol industry.
Enabled by new industrial products, the present invention has for
its purpose some copolymers in which at least three constituent
monomers have a methacrylic structure wherein the copolymers
correspond to the following general formula: ##STR3## where: B
represents Na, K, NH.sub.4, or ##STR4## R.sub.1 and R.sub.2,
identical or different, represent an atom of hydrogen or the
radical--(X--OH;
X represents an alkylene radical, branched or unbranched, having
from 1 to 3 carbon atoms or an alkylene radical, branched or
unbranched, substituted by at least one hydroxymethyl;
M represents at least one typical unsaturated monomer of the group
consisting of: the acrylamides or methacrylamides substituted on
the nitrogen by an alkyl radical, branched or unbranched, the
acrylates
or methacrylates of monoalkyl ether of ethylene glycol or of
polyethylene glycol, and N-vinyl pyrrolidone;
X is from 22% to 64% in moles;
y is from 13% to 73% in moles;
z is from 6% to 23% in moles; and v is from 0% to 22% in moles;
x+y+z+v being equal to 100%.
According to the invention the acrylamides or methacrylamides
substituted on the nitrogen by a branched or unbranched alkyl
radical correspond to the following formula: ##STR5## where:
R.sub.3, R.sub.4, and R.sub.5, identical or different, represent
either a hydrogen atom or a methyl radical; and
R.sub.6 is an alkyl radical, branched or unbranched, having from 1
to 11 carbon atoms.
Among the compounds of formula II above one can cite in particular:
N-tertiobutyl acrylamide, N-octyl acrylamide, N-decyl acrylamide,
N-dodecyl acrylamide, N-(dimethyl-1,1 propyl-1) acrylamide,
N-(dimethyl-1,1 butyl-1) acrylamide, N-(dimethyl-1,1 pentyl)
acrylamide, as well as the corresponding methacrylamides.
According to the invention, the acrylates or methacrylates of
monoalkylether of ethylene of polyethylene glycol correspond to the
following formula: ##STR6## where: R.sub.3 has the same
significance as in formula II;
R.sub.7 represents a methyl or ethyl radical; and
n is an integer between 1 and 12.
Among the compounds of formula III one can cite in particular the
acrylates and methacrylates of monomethyl or ethyl ether of
ethylene or diethylene glycol, and the acrylates and methacrylates
of .omega.-methyl or ethyl polyethylene glycol, and in particular
among the latter, the acrylate of formula III in which radical
R.sub.7 represents a methyl radical and n=7, this acrylate being
commercialized by Union Carbide Co. under the trade name of
Carbowax-550.
Among the organic or inorganic bases susceptible of leading to
embodiments of formula Ia of the copolymer of formula I of the
invention, one can cite the following: sodium hydroxide, potassium
hydroxide, ammonium hydroxide, and amino-alcohols including
monoethanolamine; diethanolamine; triethanolamine;
isopropanolamine; diisopropanolamine; tri(hydroxy-2propyl-1) amine,
sold under the trade name of "tri-isopropanolamine" by
Ugine-Kuhlman Co.; amino-2 methyl-2 propanol-1; amino-2 methyl-2
propanediol-1,3; and amino-2 hydroxymethyl-2 propanediol-1,3.
Generally, the copolymer of the invention have molecular weights
between 10,000 and 1,500,000, and usually between 15,000 and
200,000.
Likewise, an object of the present invention consists of the
process of preparation of the new copolymers of the invention.
According to a first embodiment, the copolymers of the invention
have been obtained in working out for the first time the
copolymerization of a mixture (i) of N,N-dimethylamino-2 ethyl
methacrylate, (ii) methyl methacrylate, (iii) methacrylic acid, and
(iv) possibly at least one other monomer corresponding to the
radical M, and in then neutralizing the free carboxylic acid
functions of the copolymer with the aid of an organic or inorganic
base chosen among those mentioned above. This procedure is
completely suitable, particularly when the base is an inorganic
base like sodium hydroxide, potassium hydroxide, or ammonium
hydroxide.
According to another embodiment, the copolymers of the invention
can be obtained by copolymerizing a mixture of (i)
N,N-dimethylamino-2 ethyl methacrylate; (ii) methyl methacrylate;
(iii) methacrylic acid in its salt form, e.g., by reaction with an
amino-alcohol of the formula: ##STR7## where: R.sub.1, R.sub.2, and
X have the same significance as previously; and (iv) possibly at
least one other monomer corresponding to the radical M.
Thus this procedure consists first in the preparation of an
ammonium methacrylate the formula: ##STR8## where: R.sub.1,
R.sub.2, and X have the same significance as above through the salt
formation of methacrylic acid by reaction with an amino-alcohol of
formula IV corresponding to the salt required.
This reaction is performed preferably in an organic solvent such as
ethyl ether or alcohol at an ambient temperature 0.degree. C. to
20.degree. C.
After obtaining the ammonium salt, the latter is then copolymerized
in the presence of other monomers.
Among the different ammonium methacrylates of formula V can be
cited in particular: the methacrylate of (hydroxy-1 methyl-2)
propyl-2 ammonium, the methacrylate of (dihydroxy-1,3 methyl-2)
propyl-2 ammonium, and the methacrylate of tri((hydroxy-2)
propyl-1) ammonium.
This process of copolymerization in which the methacrylic acid is
made to occur in the salt form is particularly advantageous when
one desires to obtain a copolymer no longer containing any free
carboxylic acid function.
In fact, according to the second method described above, one cannot
be certain of obtaining total neutralization of the set of
carboxylic acid functions after the copolymerization, and thus the
copolymer obtained can possibly present certain residual odors
because of the use as monomer of a portion of the methacrylic
acid.
Nevertheless, with the exception of the odor problem, there are not
any appreciable differences in the properties of the copolymers
obtained from either process.
Whatever process is used for the preparation of the copolymers of
the invention, the copolymerization itself is performed with
classical methods, i.e., in solution in a solvent, either in mass,
or even in suspension in an inert liquid, or in an emulsion. A
further procedure includes polymerization by precipitation which
consists in using a solvent in which the monomers are soluble but
in which the polymers precipitate. According to this process the
polymer is isolated by filtration. The solvents appropriate for
this type of polymerization include cyclohexane, methylethylketone,
heptane, ethyl acetate, etc. The catalysts used are generators of
free radicals such as azo-bis-isobutyronitrile, peresters, or
oxidation-reduction systems. Among the peresters can be mentioned
in particular tertiobutyl ethyl-2 perhexanoate and tertiobutyl
perpivalate. Among the oxidation-reduction systems one can cite in
particular the aqueous couples of oxygenated ferrous chloride,
persulfate of ferrous ammonium chloride, etc.
The quantity of catalyst generally comprises between 0.1% and 6% by
total weight of the monomers used for copolymerizing.
In certain cases, copolymerization can likewise be brought about or
simply activated by means of irradiation.
The copolymerization reaction is generally performed by heating
under nitrogen and agitation at a temperature about 55.degree. C.
to 85.degree. C.
The duration of heating is preferably between 6 and 24 hours.
When according to the invention one uses the process consisting of
preparing first an ammonium methacrylate of formula V, after its
formation the latter is not isolated, but is immediately
copolymerized with other monomers in the reaction medium used in
its preparation.
In the latter case the solvent is preferably an alcohol, and
especially ethanol.
The present invention similarly has for its object, new industrial
products based on a cosmetic composition containing from 0.5% to
10% by weight at least of a copolymer of formula I and in the form
of a lacquer or a waving lotion, or again in the form of a shampoo,
a tint, or of a treatment lotion applied before or after shampooing
or tinting.
Waving lotions of the invention present themselves in the form of
aqueous or hydroalcoholic solutions containing from 20% to 70%
alcohol and have a concentration of copolymer comprising between 1%
and 3% by weight.
The alcohols generally used for such waving lotions are preferably
lower aliphatic alcohols of low molecular weight, such as ethanol
or isopropanol.
These waving lotions can in addition contain diverse adjuncts such
as plastifiers, perfumes, and colorings.
The lacquers for the hair of the invention are obtained by placing
in solution in an alcohol at least one copolymer as defined
previously, this solution being placed in an aerosol bomb and mixed
with a propellant agent.
According to this form of embodiment, the copolymer is generally
present in a proportion comprising between 0.5% and 10% by
weight.
The lacquers likewise can contain a third-part solvent that can be
present in a proportion between 3% and 35% by weight.
The alcohol, which can be either ethanol or isopropanol, generally
is present in a propellant between 5% and 80%, and preferably
between 6% and 69.5% by weight.
Among the third-part solvents that can be used in the lacquers one
can cite in particular methylene chloride, trichloroethane, ethyl
chloride, acetone, ethyl acetate, and dichlorodifluoroethane.
As propellant agents one can use fluorochloric hydrocarbons either
alone or in a mixtire such as that known under the trade name of
Freon; in particular, Freon 11, 12, 22, and 142b. Similarly, one
can use as propellant agent carbon dioxide or nitrous oxide, or
hydrocarbons such as propane, butane, isobutane, etc., these
propulsants being used either alone or mixed together, or with one
or several Freon mixtures such as those mentioned above. According
to a preferred embodiment, the Freons are employed in combination
with carbon dioxide or nitrous oxide.
According to a variant of the invention, the copolymers of formula
I similarly can be used in compositions of the invention in
association with other polymers of anionic or cationic character,
the compositions appearing then in the form of creams, gels,
emulsions, etc.
In this embodiment the polymer with anionic or cationic character
is present in the composition at a concentration between 0.01% and
10%, and preferably between 0.02% and 5%.
The compositions of the invention can contain, or course, in
addition, other ingredients such as those generally used in
cosmetics, such as plastifiers, brilliantines, perfumes, colorings,
restructuring agents, and some anionic, cationic, or non-ionic
massaging agents.
Finally, the present invention has for its object a process for
waving hair. According to this procedure, one applies on the hair
at least one waving lotion such as described above before rolling
the hair on waving rollers (of diameter 15 to 30 mm), and one then
submits the hair to drying (at temperatures of the order of
25.degree. C. to 55.degree. C.).
The amount applied to the hair depends on the volume of the head,
but is generally of the order of 10 to 100 cm.sup.3, and preferably
of the order of 20 to 50 cm.sup.3.
Finally, to improve the understanding of the invention, several
examples of preparation of the copolymers of the invention as well
as several nonlimiting examples of cosmetic compositions based on
these copolymers will now be described.
EXAMPLES
EXAMPLE I
(a) Preparation of methacrylate of (hydroxy-1 methyl-2) propyl-2
ammonium.
In a round-bottom flask of 250 ml provided with a refrigerant and
mechanical agitation, one introduces 50 g of ethyl ether and 10 g
(0.112 moles) of amino-2 methyl-2 propanol-1. The solution is
refrigerated at 0.degree. C. in an ice bath until the
stoichiometric quantity of methacrylic acid (9.65 g) to neutralize
completely the amino alcohol is introduced under vigorous
agitation. The methacrylic of (hydroxy-1 methyl-2) propyl-2
ammonium precipitates in the form of a white powder that is
filtered and dried at 20.degree. C. under reduced pressure. Yield:
100%.
According to the same mode of operation described above, one has
similarly prepared, starting with amino-2 methyl-2 propanediol-1,3,
the methacrylate of (dihydroxy-1,3 methyl-2) propyl-2 ammonium, and
beginning with "tri-isopropanolamine," the methacrylate of
tri(hydroxy-2) propyl-1) ammonium.
(b) Preparation of the copolymer of N,N-dimethylamino-2 ethyl
methacrylate (38%) methyl methacrylate (48%), and (hydroxy-1
methyl-2) propyl-2 ammonium methacrylate (14%) (in moles)
In a 1-liter reactor provided with a refrigerant, mechanical
agitation, and a nitrogen inflow, one introduces 60 g of absolute
ethanol, 36.2 g (0.362 mole) of methyl methacrylate, 45.3 g (0.288
mole) of N,N-dimethylamino-2 ethyl methacrylate, 18.5 g (0.106
mole) of (hydroxy-1 methyl-2)propyl-2 ammonium methacrylate, and 1
g of azo-bis-isobutyronitrile in solution in 100 g of absolute
ethanol. The reaction mixture is then heated at 75.degree. C. under
agitation for 8 hours. The polymer obtained with a quantitative
yield is soluble in absolute ethanol. Viscosity: 1.96 cp in 5%
solution in dimethylformamide at 34.6.degree. C.
EXAMPLE II
Preparation of the copolymer of N,N-dimethylamino-2 ethyl
methacrylate (48%), methyl methacrylate (41%), and (hydroxy-1
methyl-2) propyl-2 ammonium methacrylate (11%) (in moles).
As in example Ib described above, one similarly has copolymerized
30 g (0.3 mole) of methyl methacrylate, 55 g (0.35 mole) of
N,N-dimethylamino-2 ethyl methacrylate, and 15 g (0.086 mole) of
(hydroxy-1 methyl-2) propyl-2 ammonium methacrylate.
The polymer obtained presents a viscosity of 1.90 cp in 5% solution
in DMF at 34.6.degree. C.
EXAMPLE III
Preparation of the copolymer of N,N-dimethylamino ethyl
methacrylate (56%) methyl methacrylate (29%), (hydroxy-1 methyl-2)
propyl-2 ammonium methacrylate (15%) (in moles).
This polymer similarly has been obtained according to the procedure
described in example Ib above my proceeding with the
copolymerization of: 20 g (0.2 mole) of methyl methacrylate, 62 g
(0.395 mole) of N,N-dimethylamino-2 ethyl methacrylate, and 18 g
(0.103 mole) of (hydroxy-1 methyl-2) propyl-2 ammonium
methacrylate.
The copolymer obtained shows a viscosity of 2.00 cp in 5% solution
in DMF at 34.6.degree. C.
EXAMPLE IV
Preparation of the copolymer of N,N-dimethylamino-2 ethyl
methacrylate (31.5%), methyl methacrylate (41%), (hydoxy-1
methyl-2) propyl-2 ammonium methacrylate (17%), and
N-tertiobutylacrylamide (10.5%) (in moles).
In a round-bottom flask provided with a refrigerant, mechanical
agitation, and nitrogen inflow, one introduces 37 g of
N,N-dimethylamino-2 ethyl methacrylate, 30.5 g of methyl
methacrylate, 22.5 g of (hydroxy-1 methyl-2) propyl-2 ammonium
methacrylate, 10 g of N-tertiobutyl acrylamide, and 0.4 g of
azo-bis-isobutyronitrile in solution in 125 g of absolute ethanol.
The reaction mixture is then heated under agitation at 78.degree.
C. for about 8 hours.
The copolymer obtained is soluble in absolute ethanol. Viscosity:
2.35 cp in 5% solution in DMF at 34.6.degree. C.
EXAMPLE V
Preparation of the copolymer of N,N-dimethylamino-2 ethyl
methacrylate (30%), methyl methacrylate (35%), (hydroxy-1 methyl-2)
propyl-2 ammonium methacrylate (14%), and N-pyrrolidone (21%) (in
moles).
According to example IV described above, one similarly
copolymerizes 27 g of methyl methacrylate, 36.5 g of
N,N-dimethylamino-2 ethyl methacrylate, 18.5 g of (hydroxy-1
methyl-2) propyl-2 ammonium methacrylate, and 18 g of
N-vinylpyrrolidone in the presence of 1 g of
azo-bis-isobutyronitrile in 100 g of absolute ethanol.
The polymer obtained shows a viscosity of 2.07 cp in 5% solution in
dimethylformamide (DMF) at 34.6.degree. C.
EXAMPLE VI
In this example one describes the preparation of a copolymer of the
invention by the process consisting of a first period of preparing
the polymer in free-acid form, and of a second period of
neutralizing the carboxylic acid functions by an organic or
inorganic base.
(a) Preparation of the copolymer of N,N-dimethylamino-2 ethyl
methacrylate (38.6%), methyl methacrylate (42.5%), methacrylic acid
(14.4%), and N-tertiobutyl acrylamide (4.8%) (in moles).
In a 1-liter round-bottom flask provided with a refrigerant,
mechanical agitation, and nitrogen inflow, one introduces 50 g of
N,N-dimethylamino-2 ethyl methacrylate, 35 g of methyl
methacrylate, 10 g of methacrylic acid, 5 g of
N-tertiobutylacrylamide, and 1 g of azo-bis-isobutyronitrile in
solution in 200 g of absolute ethanol. The reaction mixture finally
is heated at 75.degree. C. under agitation for 8 hours.
The copolymer is obtained with a quantitative yield. Viscosity:
2.02 cp in 5% solution in DMF at 34.6.degree. C.
(b) The copolymer obtained according to example VIa above, after
having been placed in solution in ethanol, is neutralized with the
stoichiometric quantity of amino-2 methyl-2 propanol-1.
The copolymer thus obtained shows a viscosity of 1.78 cp in 5%
solution in dimethylformamide at 34.6.degree. C.
The copolymer obtained according to this example can be used
directly in ethanol solution for the embodiment of cosmetic
compositions using this solvent as medium.
EXAMPLES VII to XXI
According to the same operating mode as that described above in
examples VIa and VIb, one similarly prepares the copolymers of the
invention assembled into table I following.
TABLE I
__________________________________________________________________________
(Stub column) EXAMPLE VII VIII IX X XI XII XIII XIV XV XVI XVII
XVIII XIX XX XXI
__________________________________________________________________________
Methacrylate of N,N-dimethyl- amino-2 ethyl 50 59 55 60 50 42 35 42
42 45 42 42 42 33,5 40 Methacrylate of methyl 40 33 35 30 25 33 40
36 34 25 39 34 42 44,5 31 Methacrylic acid 10 8 10 10 10 10 10 12
12 15 14 12 10,7 11 10 N-tertiobutyl acrylamide 15 15 15 10 12 15 5
12 Acrylate of formula III in which: R.sub.3 = H, R.sub.7 =
CH.sub.3, and n = 12 5,3 11 N-vinylpyrrolidone 19
Azo-bis-isobutyronitrile (catalyst) 1 1 1 1 0,7 0,6 1 0,5 0,4 0,4
0,4 0,2 1 1 1 Viscosity of the copolymer 2,38 2,5 2,25 2,30 2,27
2,45 2,70 2,48 2,63 4,05 2,38 3,80 2,42 2,48 3,09 Acid index 64,4
65,9 66 64 58,3 63,8 63,3 70,4 70,8 83,0 80,5 70,0 65,5 66,1 65,2
Ethanol 200 200 200 200 100 100 100 150 150 100 150 100 100 100 100
Amino alcohol (sufficient quantity required for neutralization) a a
a a a a a a a a a a a a a Viscosity of the copolymer neutralized
1,78 1,95 1,85 2,00 2,15 2,52 2,65 2,41 2,51 3,82 2,44 3,72 2,45
2,36 2,85
__________________________________________________________________________
Footnotes: a = amino2 methyl2 propanol1 The quantities of the
monomers, of the catalyst, and of ethanol are expressed by weight.
The duration of the polymerization is about 8 hours. Viscosity was
measured in 5% solution in dimethylformamide at 34.6.degree C., and
values are expressed in centipoise (cp).
EXAMPLES OF COMPOSITIONS
EXAMPLE 1
One prepares according to the invention an aersol lacquer by mixing
the following ingredients:
______________________________________ Polymer obtained according
to example I 6.5 g Perfume 0.2 g Ethanol (sufficient quantity) 100
g ______________________________________
25 g of this composition are packaged in an aerosol bomb with 45 g
of trichlorotrifluoromethane and 30 g of
dichlorodifluoromethane.
EXAMPLE 2
One prepares according to the invention a waving lotion by mixing
the following ingredients:
______________________________________ Polymer obtained according
to example III 2 g Perfume 0.1 g Ethanol 45 g Water (sufficient
quantity) 100 g ______________________________________
EXAMPLE 3
One prepares according to the invention a waving lotion by mixing
the following ingredients:
______________________________________ Copolymer obtained according
to example IV 2 g Perfume 0.1 g Ethanol 45 g Water (sufficient
quantity) 100 g ______________________________________
EXAMPLE 4
One prepares according to the invention an aerosol lacquer by
mixing the following ingredients:
______________________________________ Copolymer obtained according
to example V 6.5 g Perfume 0.2 g Ethanol (sufficient quantity) 100
g ______________________________________
25 g of this composition are packaged in an aerosol bomb with 45 g
of trichlorotrifluoromethane (Freon-11) and 30 g of
dichlorodifluoromethane (Freon-12).
EXAMPLE 5
One prepares according to the invention an aerosol lacquer by
mixing the following ingredients:
______________________________________ Copolymer obtained from
example XVIII 2 g Perfume 0.06 g Ethanol 38 g Freon-142b 10 g
Carbon dioxide gas (sufficient quantity) 8 bars
______________________________________
EXAMPLE 6
One prepares according to the invention an aerosol lacquer by
packaging in a bomb the following ingredients:
______________________________________ Copolymer prepared according
to example XI 2 g Ethanol 42 g Methylene chloride 20 g Propellant
(35% propane, 65% butane, sufficient quantity) 3.2 Kg
______________________________________
EXAMPLE 7
One prepares according to the invention an aerosol lacquer by
conditioning in a bomb the following ingredients:
______________________________________ Copolymer obtained according
to example XIV 2 g Ethanol 42 g Methylene chloride 35 g Propellant
agent: 35% propane, 65% butane, (sufficient quantity) 3.2 Kg
______________________________________
EXAMPLE 8
One prepares according to the invention an aerosol lacquer packaged
in a bomb with the following ingredients:
______________________________________ Copolymer obtained according
to example XVIII 2 g Ethanol 25 g Methylene chloride 35 g
Propellant agent: 35% propane, 65% butane (sufficient quantity) 3.2
Kg ______________________________________
EXAMPLE 9
One prepares according to the invention an aerosol lacquer by
mixing the following ingredients:
______________________________________ Copolymer obtained according
to example XVIII, but neutralized with tri-isopropanolamine 8.8 g
Plastifier ("Fluid 2 C-190" sold by Dow Corning Co.) 0.16 g
Methylene chloride 60 g Ethanol (sufficient quantity) 100 g
______________________________________
25 g of this composition are packaged in an aerosol bomb with 75 g
of a mixture of 50% Freon-11 and 50% Freon-12.
EXAMPLE 10
One prepares according to the invention an aerosol lacquer by
mixing the following ingredients:
______________________________________ Copolymer obtained according
to example XIV 7.6 g Plastifier (Rhodorsil 70.633 V 30, sold by the
Rhone-Poulene Co. 0.2 g Ethanol (sufficient quantity) 100 g
______________________________________
22 g of this composition are packaged in an aerosol bomb with 78 g
of a mixture of 61.5% Freon-11 and 38.5% Freon-12.
EXAMPLE 11
One prepares according to the invention an aerosol lacquer by
mixing the following ingredients:
______________________________________ Copolymer obtained according
to example XVIII 5.2 g Plastifier (Solulan 16, sold by the Amerchol
Co.) 0.25 g Ethanol (sufficient quantity) 100 g
______________________________________
30 g of this composition are packaged in an aerosol bomb with 70 g
of a mixture of 50% Freon-11 and 50% Freon-12.
EXAMPLE 12
One prepares according to the invention an aerosol lacquer by
packaging in a bomb the following ingredients:
______________________________________ Copolymer obtained according
to example XIV 2.5 g Ethanol 50 g Methylene chloride 20 g
Propellant agent: 35% propane, 65% butane 30 g
______________________________________
EXAMPLE 13
One prepares according to the invention a shampoo by mixing the
following ingredients:
______________________________________ Copolymer obtained according
to example VII, neutralized with sodium hydroxide 0.103 g Polymer
prepared according to example Xb of French Pat. No. 77 06031 0.897
g Triethanolamine laurylsulfate 10 g Water (sufficient quantity)
100 g ______________________________________
The shampoo is left in contact with the hair for 15 minutes before
rinsing, making the hair bright and soft to the touch.
EXAMPLE 14
One prepares according to the invention a shampoo by mixing the
following ingredients:
______________________________________ Copolymer obtained according
to example XV, neutralized with sodium hydroxide 0.6 g Resin
Gantrez-ES 425, sold by the General Anilin Film Corp., neutralized
with sodium hydroxide 0.4 g A compound of formula: ##STR9## 10 g
Hydrochloric acid (sufficient quantity) pH = 7 Water (sufficient
quantity) 100 g ______________________________________
One applies the shampoo obtained above for 15 minutes before
rinsing the hair, which is bright and soft to the touch.
EXAMPLE 15
One prepares according to the invention the following shampoo by
mixing the following ingredients:
______________________________________ Copolymer prepared according
to example XV, neutralized with sodium hydroxide 0.5 g Polymer of
methacrylic acid, sold by Allied Colloids Corp. under the trade
name Versicol-K11, neutralized with sodium hydroxide 0.3 g A
compound of the formula: ##STR10## 10 g Hydrochloric acid
(sufficient quantity) pH = 7 to 9 Water (sufficient quantity) 100 g
______________________________________
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